Cellular polyalkylene-etherglycolorganic diisocyanate reaction product and method of preparing same



United. States Patent r CELLULAR PGLYALKYLENE ETHERGLYCOL- ORGANIC DIISOCYANATE REACTION PROD- UCT AND METHOD OF PREPARING SAME Frank M. Brower, Midland, Mich, assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Dec. 5, 1957, Ser. No. 700,754

11 Claims. (Cl. 260-2.5)

This invention relates to vesiculated polymeric products in the molecular structure of which are recurring urethan linkages. More particularly, the invention pertains to cellular or forarninous compositions having predominantly interconnected cells and derived from the polymeric reaction product of certain polyalkylene ether glycols and certain organic diisocyanates and to a method of making the same.

This application is a continuation-in-part of a copending application, Serial No. 378,409, filed September 3, 1953. a

It is known that organic substances containing two or more isocyanate groups are capable of reacting with organic substances containing two or more hydroxyl radicals to produce polymeric substances in which the polymer molecules contain recurring urethan linkages resulting from the interreaction of an isocyanate group with an hydroxyl group. This reaction has been applied to simple diols such as ethylene glycol. It has also been applied to diols such as the hydroxy-terminated polyesters, i.e. reaction products ofpolycarboxylic acids, especially dibasic acids, with diols such as glycols in excess so that the molecules of the resulting polyesters end predominately in hydroxyl groups. For the purpose of making such polymeric materials, the isocyanate compound and the hydroxy-compound are usually reacted in approximately stoichiometric proportions.

It has now been discovered that the polymeric polyurethan reaction products of polyalkylene ether glycols having a molecular weight of at least 500 and a molecular excess of certain organic diisocyanate compounds can be caused to foam by the addition of water in the particular manner set forth hereinafter to produce tough, resilient, spongy products.

'An object of this invention is to provide cellular polymeric products, particularly ones in which the polymeric material is a polyurethan.

Another object is to provide such products in which the polyurethan is derived from polyalkylene ether glycols and organic diisocyanates.

A further object is to provide such cellular products wherein the cells are predominantly interconnecting.

Another object is to-provide means and method for making such cellular products. I I Other objects and advantages of the invention Will be apparent in the following description.

The objects of this invention are attained by reacting (a) an organic diisocyanate compound and (b) a poly: alkylene ether glycol having an average molecularweight of at least 500, continuing the reaction until the reacting mixture has a viscosity value within a particular range as set forth below, thereupon intimately mixing'with such reacting mixture (0) a small amount or" water, and allowcomm rigid, arereadfly wettable, and are capable of g .per molecular proportion of the polyalkylene ether-g1 starting material, and further corresponds'to 2,911,330 r Patented Mar. 28,196l

ice

absorbing water like a sponge. ,These foamed poly urethan compositions contain recurring ether linkages rather than carboxylic ester linkages. The cells in these foamed polyurethan compositions are, for the most part, open and inter-communicating rather than being discrete and isolated. The structure is rubbery and'elastic, being compressible yet resilient, the compressed mass returning to the expanded condition when released. The polyurethan compositions are readily wettable by water and aqueous liquids, and readily absorb such liquids into the open, cellular, spongy structure. Other features of the invention will be apparent from the following description.

The particular polyether glycols required by this invention are polyalkylene ether glycols, e.g. polyethylene ether glycol, polypropylene ether glycol and polybutylene ether glycol, having an average molecular weight of at least 500, e.g. from 500 to 10,000. Such polyalkylene ether glycols are commonly obtained by condensation of the corresponding alkylene oxide with water or with the corresponding alkylene glycol or with a lower molecular weight polyalkylene ether glycol, and consist of molecules having recurring alkoxy units and terminated with hydroxyl radicals. Mixed polyalkylene ether glycols, i.e. polyether glycols prepared from mixtures of alkylene oxides, or mixtures of polyaklylene ether glycols can be employed.

While any organic isocyanate compound is capable of reaction with the polyalkylene ether glycols described above, the organic diisocyanate compoundshaving no other reactive group, i.e. organic compounds having two isocyanate radicals and reactive with hydroxyl radicals only through the isocyanate radicals, are preferred. Such organic diisocyanate compounds can be represented by the formula O=C=NRN=C=O wherein R represents an interveningorganic linkage having no substituents, other than the two isocyanate radi Y cals, reactive with hydroxyl radicals. Exampleso-f such organic diisocyanate compounds are the polymeth'ylene .diisocyanates, such as hexamethylene diisocyanate and glycol and of the organic diisocyanate compound which, i

are admixed in the preparation of the productsof'this; invention are in part dependent on the kind of suchre- H actants employed and in part dependent on the kind of p 1 product desired. In general, larger weight proportions of the diisocyanate compound are required forfpolyH alkylene ether glycols of lower mo-lecularweight than are required for polyalkylene ether glycols of higherf molecular weight. Larger proportions of diisocyanate, compound are required to produce low density foams than are required for less expanded, higher density foam In general, larger proportions of diisocyanate compo give rise to firmer foams while, conversely, lesserfipr portions of diisocyanate compound give rise to softer, less resilient foams. Preferably, the amount of the startin organic diisocyanate compoundthat is...employed,c o responds to at least two molecular proportions; thereof 50 percent by weight of the starting mixture of the organic diisocyanate compound and the polyalkylene ether glycol.

The method of making the foamed products of this invention comprises admixing and interacting the polyalkylene ether glycol and the organic diisocyanate compound and subsequently dispersing water into the reacting mixture. The polyalkylene other glycol and the organic diisocyanate compound are preferably mixed at room temperature although the mixture may be warmed if desired. In the absence of cooling, heat generated by the reaction usually causes the temperature of the mixture to rise as the reaction takes place. The temperature can be allowed to rise to about 100 C. or above, or cooling means can be employed if desired to limit the rise in temperature and to moderate the vigor of the reaction.

In many instances, the starting polyalkylene ether glycol and organic diisocyanate compound interact readily upon being intermixed. In instances where the reaction is sluggish, the rate of reaction can be increased by heating the reacting mixture, or catalysts can be added to accelerate the reaction. Suitable catalysts for use in accelerating the interaction of the starting polyalkylene ether glycol and organic diisocyanate compound are exemplified by the inorganic strong bases or base-forming materials such as the alkali hydroxides, e.g. sodium hydroxide and potassium hydroxide, alkali oxides, e.g. sodium peroxide, alkali salts of weak acids, e.g. sodium acetate and potassium oleate, and alkali alkoxides, e.g. sodium methoxide and sodium ethoxide, organic bases, particularly tertiary amines such as pyridine, N-methylmorpholin'e, and triethylamine, and peroxides such as methyl ethyl ketone peroxide, benzoyl peroxide, and hydrogen peroxide. Depending upon the efficacy of the catalyst and the degree of activation desired, the catalysts can be advantageously employed in small proportion, e.g. up to 5 percent by weight of the reaction mixture.

It has been found that treatment of the polyalkylene ether glycol with a catalytic amount of sodium peroxide prior to admixture with the diisocyanate compound is especially advantageous in accelerating the reaction and improving the quality of the foamed product without exerting any deleterious effect thereon. The treatment is usually carried out by mixing into the po-lyalkylene ether glycol a minor catalytic amount, cg. up to about 5 percent by weight of the polyalkylene ether glycol, of sodium peroxide and preferably heating the mixture to a temperature of about 80-90 C. for a short time, cg. up to about 30 minutes, and thereafter cooling again to room temperature. It is not known with certainty what chemical reactions, if any, occur during such treatment, but polyalkylene ether glycols so treated are remarkably activated for reaction with organic diisocyanate compounds. However, the treatment with sodium peroxide as just described is not essential. Polyalkylene ether glycols can be used in accordance with this invention without any catalyst, or another of the cata lysts hereinbefore described can be used to produce the novel cellular polyurethan products.

The organic diisocyanate compound and the polyalkylene ether glycol are mixed with stirring to effect prompt and intimate intermingling of the reactants. With many polyalkyiene ether glycols, e.g. ones activated by catalysts such as sodium peroxide as described above, the reaction with the organicdiisocyanate compound proceeds rapidly with evolution of heat and increase in viscosity of the reaction mixture. Continued stirring is desirable, although the vigor of agitation may be decreased after thorough mixing of the reactants has been effected.

During a period of from a few' minutes to several hours or more, depending upon the rate of reaction, the viscosity of the reacting mixture increases untilthe reaction mixture resembles a heavy syrup. The reaction is allowed to proceed until the viscosity of the reacting mixture is in the range from about 4000 to about 20,000 centipoises, particularly from 4000 to 16,000 centipoises when the rate of reaction is relatively fast and from 8000 to 20,000 centipoises when the rate of reaction is relatively slow, preferably from 8000 to 16,000 centipoises, whereupon a small amount of water is added to the reacting mixture and thoroughly and intimately mixed therewith, and the resulting mixture is allowed to foam.

A syrupy reacting mixture having a viscosity within the above-specified range is most advantageously treated with water to effect foaming thereof. If water is added to the reacting mixture when the viscosity is less than was just defined (eg. below 4000 centipoises when the reaction is relatively fast or below 8000 centipoises when the reaction is relatively slow), the gaseous carbon dioxide that is generated escapes too readily from the mixture without forming a stable cellular structure. Any foams that do result thereby are transitory and generally collapse to substantially non-cellular masses. Moreover, the resulting products are usually sticky masses. if the addition of Water is deferred until the viscosity of the reacting mixture is greater than the range above defined (cg. above 16,000 centipoises when the reaction is relatively fast or above 20,000 centipoises when the reaction is relatively slow), it is very difficult if not impossible to obtain intimate mixing of water with the reacting mixture, and the resulting cellular product, if one be obtained, is generally non-uniform and of poor quality.

The proportion of water added to the reacting polyurethan mixture should correspond to at least one mole, preferably from one to two moles, of water per mole of unreacted organic diisocyanate in that reacting mixture, but should be not more than about 20, preferably not more than 15, percent by weight of the polyurethan reaction mixture.

The added water should promptly be thoroughly and intimately mixed with the syrupy reaction mixture by vigorous agitation. Foaming begins at once and agitation is preferably discontinued immediately after the water has been dispersed in the mixture. During the foaming step, the viscosity of the mass increases, probably as a consequence of further chain lengthening and increase in the molecular weight of the polymer molecules with the formation of disubstituted urea bridges or linkages. The mass also gels, probably by crosslinking of the molecular structure. Expansion of the foam is usually complete in a few minutes.

The properties of the resulting vesiculated polymeric polyurethans depend largely on the kind and proportion of polyalkylene ether glycol and organic diisocyanate compound which were interacted. In general, the prodnets are low-density materials having many small, open, inter-connected cells. They are generally non-rigid, elastic, resilient materials resembling sponge rubber. Th'ey' readily absorb large quantities of water. Products made from polyalkylene ether glycols of higher molecular weight (requiringless organic diisocyanate compound) are usually softer and more resilient than products made from lower molecular weight polyalkylene ether glycols.

Products made from polyethylene ether glycols, particularly those of molecular weight above about 500, are soft, elastic foams. However, unlike the polypropylene ether glycol products described below, the polyethylene ether glycol products are not stable to water. For example, a polyethylene ether glycol of molecular weight about 600 reacted with an excess of m-tolylcne diisocyanate and foamed with water produces a soft, resilient,

low-density spongy foam which readily absorbs water; in contact with water, especially hot water, the mechanical structure of the polyethylene ether giycol product 'disintegrates. Such products are particularly adapted for 'usern mechanical structures as low-density, resilient holding'or spacing members which are readily removed when desired by contact with water, or as readily disposable cleaning aids, e.g. as scrubbing pads for cleaning toilet bowls.

Products made from polypropylene ether glycols, particularly those whose molecular weight is above about 500, are also soft, elastic foams. Moreover, these products are resistant to deleterious attack by water and aqueous solutions. For example, a polypropylene ether glycol of molecular weight about 750 reacted with an excess of m-tolylene diisocyanate and foamed with water produces a soft, resilient, low-density spongy foam which readily absorbs water but which is unafiected by boiling water. Such products are particularly adapted for use as washing sponges or as resilient, low-density fillers, cushions, in shock and sound dampening, and the like.

Products made from polybutylene ether glycols and higher polyalkylene ether glycols are more firm and less elastic than those made from polypropylene ether gly- 6015 while yet readily absorbing water and being unaffected thereby.

Therefore, by selection of the kind of polyalkylene ether glycol, the molecular weight of the polyalkylene ether glycol, the proportion of organic diisocyanate compound reacted therewith and the conditions of foaming, there can be obtained foamed products varying in texture from soft to firm, and differing from one another in density, resiliency and resistance to water.

Further modifications of the compositions of this invention can be made. For example, a minor amount of a .polyhydric compound such as glycerol or trimethylol propane can be added to the polyalkylene ether glycol to provide a slight amount of cross-linking during the reaction with the organic diisocyanate compound thereby making a tougher foam structure. A minor amount, e.g. up to about percent by weight, of a fibrous reinforcing material, such as short length polyamide fiber, polyester fiber, celluiosic fiber or the like, can be mixed with the polyalkylene ether glycol and thereby incorporated in the foamed product increasing its resistance to tearing and abrasion. Minor amounts of coloring materials, fillers, abrasive agents, detergents and the like can similarly be incorporated in the foamed polymeric polyurethan resins if desired.

The invention will now be illustrated by examples,

which should not be construed as limiting the invention,

in which compositions by parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 A polypropylene ether glycol having an average mo lecular weight of about 2000 was heated at .a temperature of 80 C. with 0.5 percent of its weight of sodium peroxide for a period of several minutes and thereafter was cooled to room temperature; Twelve grams of the polypropylene ether glycol so treated and four grams of m-tolylene diisocyanate were then stirred together.

between 8000 and 16,000 centipoises, one milliliter of.

water was quickly stirred into the reaction mixture and stirring was stopped. The mass began at once to foam and after a few minutes was a firm, low-density, resilient foraminous material. It was easily compressed and promptly re-expanded upon release of pressure. .The spongy product readily absorbed water which was easily squeezed out.

In other tests, an

a minimum-of one mole of water per mole of-unreacted organic diisocyanate in the reaction mixtureto a maxi V pium of approximately 20 percent of the weight of the The temperature of the reaction mixture rose gradually and the viscosity of the mixture increased. About 10 minutes after mixing the reactants, the viscosity having increased tothat of a heavy syrup and judged to be milliliter of water was thoroughly mixed in and stirring The sponge productwas unaffected by boiling-water. I

In this instance, the amount of water, employed cor-1 responded to slightly more than '6 percent of the weight of the polyurethan reaction mixture.

amountofwater was used that correspondedto from,

polyurethan reaction mixture to produce the cellular products of this invention. y

In place of the m-tolylene diisocyanate employed in the foregoing example, there can be used another'of the organic diisocyanates hereinbefore described with "substantially the same results, i.e. formation of cellular prod- .ucts having predominantly interconnecting cells.

In place of the particular polyalkylene ether glycol 'used in the foregoing example, there can .be used other polyalkylene ether glycols, as illustrated in later examples. l While the pre-treatment ,of the polyalkylene ether glycol with sodium peroxide is of interest in activating a very fast reaction of the polyalkylene ether glycol and the organic diisocyanate, such pretreatment is not essential and can be omitted. The polyalkylene ether glycolorganic diisocyanate reaction can be carried out without any catalyst, or diverse catalysts therefor can. be. employed, and the cellular products of this invention can be obtained, provided the other conditions'of this invention are met as herein described,

EXAMPLE 2 Twelve-gram portions of polypropylene ether glycol of average molecular weightabout 2000, activated by treatment with 0.5 percent by weight'sodium peroxide as described in Example 1, were separately reacted with different amounts of m-tolylene diisocyanate and foamed by addition thereto of l-ml. portions of water as described inExample l to make foamed products identified as A through G in Table I. In the table are shown the proportions of m-tolylene diisocyanate used in making each foam in terms of the percentage of m-tolylene diisocyanate in the reaction mixture thereof with the poly-; I propylene ether glycol. In each instance, the viscosity of the reacting mixture was judged to be between 8000 and 16,000 centipoises at the time of the addition of water. The table also shows the densities of the foams, and remarks are made regarding the texture of the products.

Table I m-Tolylene Density of f Foam diisocyanate, Foam, Remarks i percent gm./cc. p 1

7 -15 0.35 very soft; poor elastlcityl A 20 0.27 soft; good elasticity. 25 0.22 D0. '29 I 0.13 medium soft; good elasticity. 35 0.13 firm; good elasticity. 40 0.12 Do. 50 0.11 Do.

EXAMPLE 3 To twelve grams of polypropylene ether glycol having; an average molecularweight of about 2000 and activated with 0.5 percent of its weight of sodium peroxide as' d scribed in Example l was added 0.5 gram of fine p'olyethylene terephthalate fibers cut'to lengths of /sf to." inch. Four grams of m-tolylene diisocyanate was then stirred in. Stirring was continued until a very viscous, heavy syru'py'condition was attained, the viscosity being estimated as about 16,000 centipoises, whereupon one was discontinued. .A soft, tough, resilient low-density foam was obtained.

EXAMPLE 4 Seven .grams of polyethylene ether glycol having an average molecular weight ofabout 600 (and having .re- .ceived no activation treatment with sodium peroxide) and three grams of m -tolylenediisocyanate wereimixed and reacted untilfia viscousmixture wasobta' hose viscosity was judged to be between.[8000 nd 1 6000 centipoises, whereupon tWodrops of 'wate' wet add i and thdroughlyadmixed; with. the reactin soft, elastic foam wasproduced' 11 s an i g mm wd ttw t' n- 7 EXAMPLE A high molecular weight polybutylene ether glycol was heated with 0.5 percent of its weight of sodium peroxide at a temperature of 8090 C. for a few minutes and 2000, catalyzed by treatment with sodium peroxide) and 25 milliliters of m-tolylene diisocyanate was prepared. The viscosity of the reaction mixture was measured with a Brookfield Synchro-Lectric Viscometer, using the thereafter was cooled to room temperature. Two grams 5 3 Spmdle mtatmfi at g i i of the polybutylene ether glycol so treated, four grams of uni)- When the vlscclsclty mac F? 400 centlpolses the untreated polybutylene ether glycol and four grams (Temperature about 60 Hummers Watef was of m-tolylene diisocyanate were mixed with stirring. added thorPughly mlxed Into the 9? mlxture' After nine minutes the viscosity had become that of a Ttlle resuhmg mixture foamed to a spongy 5511mm, open heavy syrup corresponding to between 8000 and 16,000 ce-lfid structumcentipoises. One milliliter of water was thereupon thorabfJVe test a F substantlany repeated f oughly mixed in and stirring was stopped. A firm foam the viscosity of the reaction mass was allowed to rise was obtained which, while somewhat elastic, was less above 9 cefmpolses- From time to samples of elastic than those obtained from polypropylene ether the reacting mixture were removed from the reaction vesglycol. sel and were separately mixed with small amounts of EXAMPLE 6 water and were allowed to foam. Samples were taken at In a series of tests identified as tests H P several poly viscosity values of 600?; g 13300; and 11000 i centipoises, respective y. n eac instance good, openalkylene ether glycol starting materials were mixed with celled, foamed products were Obtained m-tolylene diisocyanate and allowed to react. In Table In another test, a slow reacfing mixture was prepared 1L the i i f i f gl and from 80 milliliters of polypropylene ether glycol (mo- ,33%? a t e i 2 f lecular weight 2000, lightly catalyzed by treatment with 1 i; edraacion $11K ref are ki or a trace of sodium peroxidel and milliliters of mt I i i fi fi n fi g gf z tolyiez e diisocyanate. The viscosity of the slowly react- 111 as s galiii d to, the 1m Dian; ofwe;1 cal k1 1628 mixe 25 mg mixture gradually rose while the temperature of the 3 I Hat i and P reacting m xture remained at abou t room temperature. 2 1 53 1 2 retmated b When the viscosityof the reacting mixture reached 20,000 i fi i 2 3 i t 6 C f0 ceiitipoises, 20 milliliters of water was mixed in and r i fi as: f i y a i were to the resulting mixture was allowed to foam. The resulti dih temperature and mixed the m-tolylene diisog cellullar product wasda rlelslhent sponge havlng preninant 'iiterconn cte ce s. i Q test? i the gy of poly in othei tests, it was found that the viscosity range 0 an m-to 'ne t wre g fla g he times fi f g gg i i a or from 4000 to 20,000 centipoises in the reacting mix- If/Ever In theothe; tests Shown the reactin mixture? 5 ture was critical for the purposes of this invention. When were allowed to stand at room teniperature ie between 0 the vjscoslty of reactmg mixture of polyaikylene ether 5 and 30 C Since these reactions are exothermic glycol and Omar-11c .dnsocyaliat was apliriaclably gr.ea.ter g ht s omanem'ls warming occurred in all instances than 20,000 centipoises, the intimate addition and mixing s i of the very fast reaction in test 0 th g of water was no longer possible. The resulting products selfwarmed to about C 40 were generally non-cellular or were non-uniform; the cells, if any, were usually closed, non-communicating i i g iiig gt g fg g i ifig ggz ggz giggi g cells. In instances of fast-reacting mixtures, the maxil6,000 centipoises. At these times, the indicated amounts g g a i gi ggi of vlscoslty was In the order of of water were added to the reacting mixtures and thor- 2 mp 0518f h'and it was found that the minimum oughiy and intimately mixed therewith, after which the 1 h h reaction mixtures were allowed to foam VlSCOSliy Qf e ieaction mixtures t at produced the prod- In each instance, the resulting foamed products were :fff fi g g g gig 5 ig iggg gPigfi resilient, open-celled cellular products which readily abb 1 e 1 Sorbed water cosities appreciably elow 4000 centipoises, the foamed Table 11 Test Polyalkylene Ether Glycol T1111, Catalyst 'Iemp., C Time WatIe II] m H Pozlyggopoyleiiie ether glycol, MW. 5 none .1 100 5.5 days 2 I Polypropylene,etherglycoLMM. 7 do 100 2hours-- 2 2,000, 10 ml.; M.W. 400, 5 ml. L.-. Pal gggopglcac ether glycol, MW. 5 Potassium oleate, trace Room Temp 4hours 2 i K do. f 4. 5 Triethylamine,0.5ml 100 2.25ll011IS--- 2 L ..do u ,5 N-lltethylmorpholine,lml 100 2h0urs. 2 M Pglgggoggleilie other glycol, M.W. l0 ltletllaylgghyl getoue peroxide, 1.3 Room Temp '4 days 2 U m I11 t 0 N Pozlyggopg lcne ether glycol, MW. 5 Hgtrogen Peroxide 30 percent, do 3days 3 m ro s. O Polydsiitlygeule ether glycol, MW. 5 P%t)1SSl l;.mh/'dIOXid,Tl0.C0(N011: ca.60 Zmins 2 1. m. P Po2l%ggop.yleae ether glycol, M.W. 10 Sodium metal, Trace (Note 2) Room Temp 2.6 hours.. 3

Note 1: percent solution in dimethyl pbthalete. Note 2:

Polyalkylene other glycol pretreated with catalyst before addition of rn-tolylene diisocyanate.

EXAMPLE 7 addition thereto or water.

lii one such test, a fast-reacting mixture of 80 milliliters of polypropylene ether 'glycol '(iiiolecular weight suiting products were usually tacky.

products usually at least partially collapsed, and the re- In instances of slow-reacting mixtures, it was found preferable to allow the reaction to proceed until the viscosity of the reacting mixture was at least 6000, preferably between 8000 and 20,000 centipoises before adding water thereto.

That which is claimed is:

1. A method of making a foraminous polyurethan composition having predominantly interconnecting cells, which method comprises reacting (a) an organic 'diisocyanate compound in which the two isocyanate radicals are the only groups reactive with hydroxyl radicals and (b) a polyalkylene ether glycol having an average mo lecular weight of from 500 to 10,000, the organic diisocyanate compound being present in amount corresponding to from 15 to 50 percent by weight of the resulting mixture of (a) and (b) and to at least two moles thereof per mole of the polyalkylene ether glycol, continuing the reaction between the polyalkylene ether glycol and the organic diisocyanate compound until the viscosity of the reacting mixture corresponds to from 4000 to 20,000 centipoises, thereupon intimately mixing with the reacting mixture, while the viscosity thereof corresponds to from 4000 to 20,000 centipoises, (c) water in an amount corresponding to at least one mole thereof per mole of unreacted organic diisocyanate compound in the reacting mixture and to not more than 20 percent by weight of the reacting mixture, and allowing the resulting reaction mixture to foam.

2. A method according to claim 1 wherein the polyalkylene ether glycol is a polyethylene ether glycol and the organic diisocyanate compound is m-tolylene diisocyanate.

3. A method according to claim 1 wherein the polyalkylene ether glycol is a polypropylene ether glycol and the organic diisocyanate compound is m-tolylene diisocyanate.

4. A method according to claim 1 wherein the polyalkylene ether glycol is a polybutylene ether glycol and the organic diisocyanate compound is m-tolylene diisocyanate.

5. A method of making a foraminous polyurethan composition having predominantly interconnecting cells, which method comprises reacting (a) an organic diisocyanate compound in which the two isocyanate radicals are the only, groups reactive with hydroxyl radicals and (b) a polyalkylene ether glycol having an average molecular weight of from 500 to 10,000, which polyalkylene ether glycol has been activated prior to use in this method by heating with up to 5 percent of its weight of sodium peroxide when the alkylene radicals of the polyalkylene ether glycol are larger than ethylene radicals, the organic diisocyanate compound being present in amount corresponding to from 15 to 50 percent by weight of the resulting mixture of (a) and (b) and to at least two moles thereof per mole of the polyalkylene ether glycol, continuing the reaction between the polyalkylene ether glycol and the organic diisocyanate compound until the viscosity of the reacting mixture corresponds to from 8000 to 16,000 centipoises, thereupon intimately mixing with the reacting mixture, while the viscosity thereof corresponds to from 8000 to 16,000 centipoises, (0) Water in an amount corresponding to the organic diisocyanate compound is m-tolylene diiso reacted organic diisocyanate with water in amount corresponding to at least one mole thereof per mole of unreacted organic diisocyanate and to not more than 20,

at least one mole thereof per mole of unreacted organic diisocyanate compound in the reacting mixture and to not more than 20 percent by weight of the reacting mixture, and allowing the resulting reaction mixture to V foam.

6. A method according to claim 5 wherein the polyalkylene ether glycol is a polyethylene ether glycol and cyanate.

7. A method according to claim 5 wherein the poly- 8. A method according to claim 5 wherein the polyalkylene ether glycol is a polybutylene ether glycol and the organic diisocyanate, compound is m-tolylene diisocyanate.

9. A foraminous article having predominantly interconnecting cells the walls of which consist essentially of a polyurethan condensation polymer having recurring urethan linkages formed by reaction. of reactants consisting of a polyalkylene ether glycol having an average molecular weight of from 500 to 10,000 and wherein the alkylene groups comprise substantially from 3 to 4 carbon atoms and an organic diisocyanate compound in which the two isocyanate radicals are the only groups reactive with hydroxyl radicals, the organic diisocyanate compound being used in amount corresponding to from 15 to percent by weight of the reactants and to, at least two moles thereof per mole of the polyalkylene ether glycol, the cells having been formed by further reaction of the polyurethan polymer containing unpercent by weight of the polymer-diisocyanate mixture, the water being intimately admixed with the reacting mixture of polyalkylene ether glycol and organic diisocyanate while the viscosity of said reacting mixture corre sponds to from 4000 to 20,000 centipoises.

10. A foraminous article having predominantly interconnecting cells according to claim 9 wherein the polyalkylene ether, glycol is a polypropylene ether glycol, and

the organic diisocyanate compound is m-tolylene diisocyanate.

11. A foraminous article having predominantly interconnecting cells according to claim 9 wherein the polya'lkylene ether glycol is a polybutylene ether glycol, and

the organic diisocyanate compound is m-tolylene diiso- Walter Ian. 27,,1959 p UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,977 33O March 28 1961 Frank M. Brewer It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, line 3,, for "reaction" read reacting column 9 lines 6 and 40, after "lO OOO'fl, each occurrence, insert and wherein the alkylene groups comprise from 3 to 4 carbon atoms same column 9, line 22','beginning with 2. A method according", strike out all to and including "cyanate." in line 25, same column; column 1O, line 4 beginning with "6. A method according" strike out all to and including cyanate. in line 7, same column; line 22 strike out "substantially"; columns 9 and 10,, for the claims numbered "3, 4, 5 7, '8, 9,. 10, and 11" read 2,,- 3 4 5 6,, 7 8 and 9 column 10, lines 8 and 12, for the claim reference numeral "5", each occurrence, read 4 -----3 lines 40 and 45, for the claim reference numeral "9",, each occurrence, read a in the heading to the printed specification line 9,, for "11 Claims" read 9 Claims Signed and sealed this 28th day of November- 1961,

(SEAL) Attest:

DAVID L, LAnii ERNEST w., SWIDER v Commissioner ofPatents Attesting Officer 

1. A METHOD OF MAKING A FORAMINOUS POLYURETHAN COMPOSITION HAVING PREDOMINANTLY INTERCONNECTING CELLS, WHICH METHOD COMPRISES REACTING (A) AN ORGANIC DIISOCYANATE COMPOUND IN WHICH THE TWO ISOCYANATE RADICALS ARE THE ONLY GROUPS REACTIVE WITH HYDROXYL RADICALS AND (B) A POLYALKYLENE ETHER GLYCOL HAVING AN AVERAGE MOLECULAR WEIGHT OF FROM 500 TO 10,000, THE ORGANIC DIISOCYANATE COMPOUND BEING PRESENT IN AMOUNT CORRESPONDING TO FROM 15 TO 50 PERCENT BY WEIGHT OF THE RESULTING MIXTURE OF (A) AND (B) AND TO AT LEAST TWO MOLES THEREOF PER MOLE OF THE POLYALKYLENE ETHER GLYCOL, CONTUINING THE REACTION BETWEEN THE POLYALKYLENE ETHER GLYCOL AND THE ORGANIC DIISOCYANATE COMPOUND UNTIL THE VISCOSITY OF THE REACTING MIXTURE CORRESPONDS TO FROM 4000 TO 20,000 CENTIPOISES, THEREUPON INTIMATELY MIXING WITH THE REACTING MIXTURE, WHILE THE VISCOSITY THEREOF CORRESPONDS TO FROM 4000 TO 20,000 CENTIPOISES, (C) WATER IN AN AMOUNT CORRESPONDING TO AT LEAST ONE MOLE THEREOF PER MOLE OF UNREACTED ORGANIC DIISOCYANATE COMPOUND IN THE REACTING MIXTURE AND TO NOT MORE THAN 20 PERCENT BY WEIGHT OF THE REACTING MIXTURE, AND ALLOWING THE RESULTING REACTION MIXTURE TO FOAM. 